Roman Boulatov
Assistant Professor of Chemistry
Roman Boulatov received his undergraduate degree from the University of St. Petersburg in 1996 and his Ph.D. from Stanford University in 2002. After completing his postdoctoral at Harvard University, Roman joined the University of Illinois in the spring of 2005. His research is in a highly-multidisciplinary area of energy transduction at the molecular, supramolecular, meso- and macroscopic scales. He is particularly interested in experimental synthetic studies of the basic principles of chemomechanical energy transduction.
Research
We integrate the methods of synthetic, physical and computation chemistry to understand how mechanical force affects chemical reactivity (so called mechanochemical or chemomechanical coupling). Chemomechanical coupling underlies diverse phenomena from muscle contraction and chromosomal segregation to the operation of actuating materials, to fragmentation of polymers under various circumstances, to single-molecule force spectroscopy. An outstanding question in this very active area of research is the development of models capable of predicting – with chemically meaningful accuracy – changes in the rate of a chemical reaction as a function of mechanical force acting at two or more atoms of the reactant. Such predictive capabilities are critical both for fundamental understanding of existing chemomechanical phenomena, and for rational design of new devices and processes that exploit it. Examples of the latter include propulsion systems for autonomous nanomechanical devices, new types of self-healing and actuating materials, ultra-tough protective coatings on various surfaces, methods to localize and study propagation of cracks and improvements in mechanical properties of specialty polymers.
Although traditionally chemomechanical phenomena are studied by single-molecule force spectroscopy, we rely on specially designed synthetic molecules to mimic the mechanical force exerted on a small reactant (mechanophore). Typically, we computationally design a series of 5-10 homologous molecules comprised of the mechanophore and an actuator – a molecular moiety which, upon external input of energy (often as a photon) undergoes conformational rearrangement that puts the mechanophore under mechanical stress and results in over billion-fold acceleration of the mechanophore reaction relative to that in free mechanophore. We synthesize the molecules, measure the kinetics of the mechanophore reaction and computationally model the results using the free mechanophore molecule reacting under influence of external force. The result of this approach is an atomistic model of the perturbation of chemical kinetics by mechanical force. The reactions whose mechanochemistry we study range from electrocyclic ring opening of cyclobutene to hydrolysis of pyrophosphate bonds to oxidation of the imide group of polyimide polymers.
Group members concentrate in one or more of the following areas: synthesis, kinetic studies and photochemistry, electronic structure computations and programming. The diversity of the expertise in the group make it an excellent ground for learning how to tackle modern scientific problems that transcend traditional boundaries between different areas of chemistry.
Publications
Yang, Q.; Khvostichenko, D.; Atkinson J.; Boulatov, R. "Simple Dimer Containing Dissociatively-Stable Mono-Imidazole Ligated Ferrohemes". Chem. Comm., 2008, in press. (text)
Khvostichenko, D.; Choi, A.; Boulatov, R. "DFT Calculations of the Lowest-Energy Quintet and Triplet States of Model Hemes: Effects of Functional, Basis Set and Zero-Point Energy Corrections". J. Phys. Chem. A. in press.
Khvostichenko, D.; Yang, Q.; Boulatov, R. "Simple Heme Dimers with Strongly Cooperative Ligand Binding". Angew. Chem. Int. Ed., 2007, 46, 8368-8370 (text).
Boulatov, R. "Metalloporphyrin catalysts for oxygen reduction" (invited review). In Fuel Cell Catalysis. Koper, M.; Wieckowski, A., Eds.; Wiley: New York, 2007; accepted.
Boulatov, R. "Billion Year Old Oxygen Cathode that Actually Works: Biological and Biomimetic Oxygen Reduction as an Energy Source" (invited review). In N4 Macrocyclic Metal Complexes. Zagal, J. H., Dodelet, J.-P. Eds; Kluwer: Amsterdam, 2006, Ch. 1, pp. 1-36.
Weibel, D. B.; Boulatov, R.; Lee, A.; Ferrigno, R.; Whitesides, G. M. "A Prototype of a Coal-powered Redox Fuel Cell that Operates at 100 oC". Angew. Chem. Int. Ed. 2005, 44, 5682-5686. (text).
